CN103007847A - Magnetic nanoparticle-based immobilized laccase and ionic liquid composite particle and application thereof - Google Patents
Magnetic nanoparticle-based immobilized laccase and ionic liquid composite particle and application thereof Download PDFInfo
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- CN103007847A CN103007847A CN2012105569734A CN201210556973A CN103007847A CN 103007847 A CN103007847 A CN 103007847A CN 2012105569734 A CN2012105569734 A CN 2012105569734A CN 201210556973 A CN201210556973 A CN 201210556973A CN 103007847 A CN103007847 A CN 103007847A
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Abstract
The invention discloses a magnetic nanoparticle-based immobilized laccase and an ionic liquid composite particle, a preparation method thereof and application in removal of contaminants in water. The preparation method comprises the steps that carbonyl iron is taken as an iron source and is synthesized to be gamma-Fe2O3 nano-particles through a chemical precipitation method; the magnetic nanoparticles are taken as cores, tetraethoxysilane and a silane coupling agent are taken as a silicon source, and by means of a sol-gel method, surface amino-functionalized nano core-shell type magnetic silicon dioxide is prepared; 1-ethyl-(3-dimethyllaminopropyl) carbodiie hydrochlide is taken as a coupling agent, and laccase is bonded on the surface of the nano core-shell type magnetic silicon dioxide in a covalent bond manner to obtain the immobilized laccase of the magnetic nanoparticle silicon dioxide particles; and then the immobilized laccase is reacted with a functionalized ionic liquid which is synthesized by reacting N,N-carbonyldiimidazole and an ionic carboxy contained liquid to prepare the magnetic nanoparticle immobilized laccase and ionic liquid composite particle, and the composite particle is applied to the removal of the contaminants in water.
Description
Technical field
The invention belongs to environmental protection technical field, particularly a kind of based on magnetic Nano immobilization laccase and ionic liquid composite particles and preparation method thereof and the application in the pollutant in removing water body.
Background technology
Along with the fast development of economy, water environment pollution is day by day serious, and organic pollution accumulates over a long period and exists lastingly, and serious harm is to the health of the ecosystem and the sustainable development of human society.Except hard degradation, they also have higher bio-toxicity and carcinogenic, teratogenesis, mutagenicity.Therefore, efficient, the economic New Wastewater Treatment Technique of research and development becomes the focus that whole world efforts at environmental protection person is concerned about.
Laccase is a kind of polyphenol oxidase of cupric, and the phenols that it is can catalysis a large amount of and the oxidation of aromatic amine compounds have important using value at aspects such as wastewater treatment, bio-bleaching, aromatic conversion, environmental monitorings.The protein structure of laccase has limited effective use of laccase so that the easy inactivation of laccase, reclaim problems such as being difficult to and being difficult to continuously use.One of effective measures that address these problems with the technology of being fixed of laccase.
Ionic liquid has soluble end is wide, electrochemical window is wide, good heat endurance, " zero " vapour pressure, the advantage such as easy to use, is eco-friendly green solvent.Ionic liquid has viscosity higher, in extraction during organic pollutants, two-phase interface is less, reclaim difficulty with etc. problem, limited effective use of ionic liquid.
Employing has magnetic Nano material while fixing laccase and the ionic liquid of high-specific surface area and good dispersion, not only can obviously improve the stability of laccase and the recycling rate of waterused of ionic liquid and laccase, and for laccase introducing ionic liquid is the catalysis microenvironment, can improve the reclaiming problem of laccase activity and solution ionic liquid.In removing water body, be with a wide range of applications in the field of pollutant.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, primary and foremost purpose of the present invention is to provide a kind of preparation method based on magnetic Nano immobilization laccase and ionic liquid composite particles; The method is carrier based on the magnetic Nano silicon dioxide microsphere, by the covalent bonding effect laccase and ionic liquid is fixed on this carrier; Utilize carbonyl iron to be source of iron, chemical precipitation method synthesizing magnetic γ-Fe
2O
3Nano particle; Take this magnetic nanoparticle as nuclear, ethyl orthosilicate and silane coupler are the silicon source, utilize sol-gel process to make the nano core-shell type magnetic silica of surface amino groups functionalization.Take 1-ethyl-(3-dimethylaminopropyl) carbodiimide as coupling agent, immobilization laccase makes the immobilization laccase of magnetic Nano silicon dioxide microparticle.Again with N, N-carbonyl dimidazoles (CDI) and contain the ionic liquid reaction complex functionality ionic liquid reaction of carboxyl, preparation magnetic Nano immobilization laccase and ionic liquid composite particles.
Another purpose of the present invention is to provide that a kind of said method is prepared from based on magnetic Nano immobilization laccase and ionic liquid composite particles.
A further object of the present invention is to provide the above-mentioned application in the pollutant in removing water body based on magnetic Nano immobilization laccase and ionic liquid composite particles.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method based on magnetic Nano immobilization laccase and ionic liquid composite particles comprises following operating procedure:
(1) the nano magnetic silica particulate of the surperficial amino functional of preparation: octyl ether, oleic acid and carbonyl iron are mixed; be heated to 90～140 ℃, reacted 1～4 hour, be cooled to room temperature; add the dry oxidation trimethylamine; under nitrogen protection, be heated to 120～150 ℃, react after 1～3 hour; be cooled to room temperature; add ethanol, centrifugation, gained is precipitated as magnetic γ-Fe
2O
3Nano particle; With magnetic γ-Fe
2O
3Nanoparticulate dispersed is in n-hexane, and obtaining concentration is magnetic Nano γ-Fe of 0.5g/mL
2O
3Solution; With magnetic Nano γ-Fe
2O
3Solution, polyoxyethylene nonylplenyl ether and n-hexane mix also ultrasonic dispersion 10 minutes, add ammoniacal liquor and ethyl orthosilicate, and at room temperature, stirring reaction 24～48 hours adds silane coupler again, at room temperature, and stirring reaction 12～48 hours; Centrifugation, solid phase are the nano magnetic silica particulate of surface amino groups functionalization.
(2) the nano magnetic silica particulate of surface amino groups functionalization and 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride joins in the laccase solution, and at room temperature stirring reaction is 12～48 hours; Magnetic Isolation, collecting solid phase is based on magnetic Nano silicon dioxide microparticle immobilization laccase.
(3) magnetic Nano silicon dioxide microparticle immobilization laccase and functionalized ion liquid mix, and at room temperature stirring reaction is 24 hours.Magnetic Isolation, collecting solid phase is based on magnetic Nano immobilization laccase and ionic liquid composite particles.
The volume ratio of the described carbonyl iron of step (1) and octyl ether is 1:50～1:20, and the mol ratio of described carbonyl iron and oleic acid is 1:3～1:6; The mol ratio of described carbonyl iron and dry oxidation trimethylamine is 1:3～1:5; The volume ratio of described carbonyl iron and ethanol is 1:100～1:300; The degree of polymerization of described polyoxyethylene nonylplenyl ether is 520; Described magnetic Nano γ-Fe
2O
3The volume ratio of solution, polyoxyethylene nonylplenyl ether and n-hexane is 1:(0.6～3): (12～30); Described nanometer γ-Fe
2O
3The volume ratio of solution and ammoniacal liquor, ethyl orthosilicate and silane coupler is 10:1:(3～6): (3～9); Described silane coupler is 3-aminopropyl triethoxysilane or N-β-(aminoethyl)-γ aminopropyl trimethoxysilane.
The described laccase of step (2) is lacquer tree (Rhus vernicifera), adopt suede bolt bacterium (Trametes versicolor), Corilus versicolor Quel. (Coriolus versicolor) or crinosity bolt bacterium (Trametes hispida), laccase solution is for to be dissolved in pH7.5 sodium phosphate 0.1mol/L buffer solution with laccase, and preparation laccase concentration is 20mg/mL.
The mass ratio of the nano magnetic silica particulate of the described surface amino groups functionalization of step (2), 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and laccase solution is 5:(1～3): (10～30).
The mass ratio of step (3) described magnetic Nano silicon dioxide microparticle immobilization laccase and functionalized ion liquid is 1:5～1:10.
The described functionalized ion liquid of step (3) prepares according to following operating procedure: be the N of 6:5 with mol ratio, N-carbonyl dimidazoles (CDI) and the ionic liquid that contains carboxyl mix, and under 30～50 ℃, stirring reaction is after 24 hours, be cooled to room temperature, obtain functionalized ion liquid.
The described ionic liquid that contains carboxyl is 1-carboxyethyl-3-methyl imidazolium tetrafluoroborate, 1-carboxyethyl-3-methylimidazole hexafluorophosphate, 1-carboxyethyl-3-methylimidazole trifluorosulfonimide salt, 1-carboxylic propyl group-3-methyl imidazolium tetrafluoroborate or 1-carboxylic propyl group-3-methylimidazole hexafluorophosphate.
A kind of by said method prepare based on magnetic Nano immobilization laccase and ionic liquid composite particles.
The above-mentioned application in the pollutant in removing water body based on magnetic Nano immobilization laccase and ionic liquid composite particles.
Described application is in containing the water body of pollutant, adds based on magnetic Nano immobilization laccase and ionic liquid composite particles, at room temperature reacts 4 hours; Described pollutant is dyestuff, chlorophenol or phenol.
The present invention is compared with existing technology, have following advantage and beneficial effect: the employing magnetic Nano of (1) the present invention preparation is that carrier immobilized laccase can obviously improve the stability of laccase and the recycling rate of waterused of ionic liquid and laccase, is expected to be widely used in the field of pollutant in removing water body; (2) method of the present invention is easy and simple to handle, cost is low, treatment process is simple, it is high to remove efficient.
Description of drawings
Fig. 1 is that the magnetic Nano immobilization laccase of the inventive method preparation and particle diameter and the pattern of ionic liquid composite particles adopt the transmission electron microscope phenogram.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited to this.
The concentration of pollutant adopts high effective liquid chromatography for measuring in following examples water body.
Employed functionalized ion liquid prepares according to following operating procedure in following examples: be the N of 6:5 with mol ratio, N-carbonyl dimidazoles (CDI) and the ionic liquid that contains carboxyl mix, and under 50 ℃, stirring reaction is after 24 hours, be cooled to room temperature, obtain functionalized ion liquid.The described ionic liquid that contains carboxyl is 1-carboxyethyl-3-methyl imidazolium tetrafluoroborate, 1-carboxyethyl-3-methylimidazole hexafluorophosphate, 1-carboxyethyl-3-methylimidazole trifluorosulfonimide salt, 1-carboxylic propyl group-3-methyl imidazolium tetrafluoroborate or 1-carboxylic propyl group-3-methylimidazole hexafluorophosphate.
Embodiment 1
1.0mL carbonyl iron, 20mL octyl ether are mixed with 12.9g oleic acid; be heated to 100 ℃ of reactions after 3 hours; be cooled to room temperature, add 1.7g dry oxidation trimethylamine, under nitrogen protection; be heated to 130 ℃; react after 3 hours, be cooled to room temperature, add 100mL ethanol; centrifugation is precipitated as magnetic γ-Fe
2O
3Nano particle is scattered in n-hexane with it, and obtaining concentration is magnetic Nano γ-Fe of 0.5g/mL
2O
3Solution; With 1.0mL magnetic Nano γ-Fe
2O
3Solution, 2.0mL polyoxyethylene nonylplenyl ether (degree of polymerization 520) and the ultrasonic dispersion of 20mL n-hexane 10 minutes, 0.1mL ammoniacal liquor, 0.4mL ethyl orthosilicate, at room temperature, stirring reaction 36 hours adds 0.5mL N-β-(aminoethyl)-γ aminopropyl trimethoxysilane, at room temperature, stirring reaction 24 hours, centrifugation, solid phase is the nano magnetic silica particulate of surface amino groups functionalization; Be the Che Shu lacquer enzyme solutions of 20mg/mL with nano magnetic silica particulate, 0.4g1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 20mL, the concentration of 1g surface amino groups functionalization, at room temperature stirring reaction is 24 hours; Magnetic Isolation, collecting solid phase is magnetic Nano silicon dioxide microparticle immobilization lacquer tree laccase; 1.0g magnetic Nano silicon dioxide microparticle immobilization lacquer tree laccase particulate and 5.0g functionalized ion liquid are mixed, and at room temperature stirring reaction is 24 hours; Magnetic Isolation, collecting solid phase is magnetic Nano immobilization laccase and ionic liquid composite particles, its particle diameter and pattern adopt the transmission electron microscope phenogram.Its particle diameter and pattern adopt the transmission electron microscope phenogram.Fig. 1 result shows, magnetic Nano immobilization laccase and ionic liquid composite particles are nanostructured.Be 1mg/L, contain in phenol, catechol or the resorcinol pollutant water body respectively in 100mL, concentration, add 1g magnetic Nano immobilization lacquer tree laccase and ionic liquid composite particles, at room temperature reacted 4 hours.Removal of pollutants rate (%) is as shown in table 1 in the water body, and table 1 is the result show, magnetic Nano immobilization laccase and ionic liquid composite particles can effectively be removed the pollutant in the water body.
Table 1 embodiment 1 gained composite particles is to pollutants removal rate in the water body
Embodiment 2
1.0mL carbonyl iron, 50mL octyl ether are mixed with 6.45g oleic acid; be heated to 90 ℃ of reactions after 4 hours; be cooled to room temperature, add 3.4g dry oxidation trimethylamine, under nitrogen protection; be heated to 150 ℃; react after 1 hour, be cooled to room temperature, add 300mL ethanol; centrifugation is precipitated as magnetic γ-Fe
2O
3Nano particle is scattered in n-hexane with it, and obtaining concentration is magnetic Nano γ-Fe of 0.5g/mL
2O
3Solution; With 1.0mL magnetic Nano γ-Fe
2O
3Solution, 3mL polyoxyethylene nonylplenyl ether (degree of polymerization 520) mix also ultrasonic dispersion 10 minutes with the 30mL n-hexane, add 0.1mL ammoniacal liquor and 0.3mL ethyl orthosilicate, at room temperature stirring reaction is 48 hours, add again the 0.3mL3-aminopropyl triethoxysilane, at room temperature, stirring reaction 48 hours, centrifugation, solid phase is the nano magnetic silica particulate of surface amino groups functionalization; Be the crinosity bolt bacterium laccase solution of 20mg/mL with nano magnetic silica particulate, 0.6g1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 60mL, the concentration of 3g surface amino groups functionalization, at room temperature stirring reaction is 24 hours.Magnetic Isolation, collecting solid phase is magnetic Nano silicon dioxide microparticle immobilization crinosity bolt bacterium laccase; 1.0g magnetic Nano silicon dioxide microparticle immobilization crinosity bolt bacterium laccase and 7.0g functionalized ion liquid are mixed, at room temperature, stirring reaction 24 hours.Magnetic Isolation, collecting solid phase is magnetic Nano immobilization laccase and ionic liquid composite particles, be 0.02mmol/L, contain in anthraquinone dye (reactive blue 62), azo dyes (methyl red) or triarylmethane dye (bromocresol green) the pollutant water body respectively in 100mL, concentration, add 1g magnetic Nano immobilization laccase and ionic liquid composite particles, at room temperature reacted 4 hours.Removal of pollutants rate (%) is as shown in table 2 in the water body, and table 2 is the result show, magnetic Nano immobilization laccase and ionic liquid composite particles can effectively be removed the pollutant in the water body.
Table 2 embodiment 2 gained composite particles are to pollutants removal rate in the water body
Embodiment 3
1.0mL carbonyl iron, 30mL octyl ether are mixed with 10.75g oleic acid; be heated to 140 ℃ of reactions after 1 hour; be cooled to room temperature, add 2.3g dry oxidation trimethylamine, under nitrogen protection; be heated to 120 ℃; react after 3 hours, be cooled to room temperature, add 160mL ethanol; centrifugation is precipitated as magnetic γ-Fe
2O
3Nano particle is scattered in n-hexane with it, and obtaining concentration is magnetic Nano γ-Fe of 0.5g/mL
2O
3Solution; With 1.0mL magnetic Nano γ-Fe
2O
3Solution, 3.0mL polyoxyethylene nonylplenyl ether (degree of polymerization 520) mix also ultrasonic dispersion 10 minutes with the 30mL n-hexane, add 0.1mL ammoniacal liquor and 0.6mL ethyl orthosilicate, at room temperature, stirring reaction 24 hours, add again 0.9mLN-β-(aminoethyl)-γ aminopropyl trimethoxysilane, at room temperature, stirring reaction 12 hours, centrifugation, obtaining solid phase is the nano magnetic silica particulate of surface amino groups functionalization; With nano magnetic silica particulate, 0.6g1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 30mL, the concentration of 1g surface amino groups functionalization be 20mg/mL adopt suede bolt bacterium laccase solution, at room temperature stirring reaction is 24 hours.Magnetic Isolation, collecting solid phase is that suede bolt bacterium laccase is adopted in the immobilization of magnetic Nano silicon dioxide microparticle; Suede bolt bacterium laccase particulate and the mixing of 10g functionalized ion liquid are adopted in the immobilization of 1.0g magnetic Nano silicon dioxide microparticle, and at room temperature stirring reaction is 24 hours; Magnetic Isolation, collecting solid phase is magnetic Nano immobilization laccase and ionic liquid composite particles.Be 0.02mmol/L, contain in the pollutant water bodys such as o-chlorphenol, m-Chlorophenol or parachlorophenol respectively in 100mL, concentration, add 1g magnetic Nano immobilization laccase and ionic liquid composite particles, at room temperature reacted 4 hours.Removal of pollutants rate (%) is as shown in table 3 in the water body, and table 3 is the result show, magnetic Nano immobilization laccase and ionic liquid composite particles can effectively be removed the pollutant in the water body.
Table 3 embodiment 3 gained composite particles are to pollutants removal rate in the water body
Embodiment 4
1.0mL carbonyl iron, 40mL octyl ether are mixed with 8.6g oleic acid; be heated to 120 ℃ of reactions after 2 hours; be cooled to room temperature, add 2.8g dry oxidation trimethylamine, under nitrogen protection; be heated to 140 ℃; react after 2 hours, be cooled to room temperature, add 240mL ethanol; centrifugation is precipitated as magnetic γ-Fe
2O
3Nano particle is scattered in n-hexane with it, and obtaining concentration is magnetic Nano γ-Fe of 0.5g/mL
2O
3Solution; With 1.0mL magnetic Nano γ-Fe
2O
3Solution, 1.2mL polyoxyethylene nonylplenyl ether (degree of polymerization 520) mix also ultrasonic dispersion 10 minutes with the 24mL n-hexane, add 0.1mL ammoniacal liquor and 0.5mL ethyl orthosilicate, at room temperature, stirring reaction 36 hours, add again the 0.7mL3-aminopropyl triethoxysilane, at room temperature, stirring reaction 24 hours, centrifugation, solid phase are the nano magnetic silica particulate of surface amino groups functionalization; Be the Corilus versicolor Quel. laccase solution of 20mg/mL with nano magnetic silica particulate, 0.2g1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 10mL, the concentration of 1g surface amino groups functionalization, at room temperature stirring reaction is 24 hours; Magnetic Isolation, collecting solid phase is magnetic Nano silicon dioxide microparticle immobilization Corilus versicolor Quel. laccase.1.0g magnetic Nano silicon dioxide microparticle immobilization Corilus versicolor Quel. laccase particulate and 9.0g functionalized ion liquid are mixed, and at room temperature stirring reaction is 24 hours.Magnetic Isolation, collecting solid phase is magnetic Nano immobilization laccase and ionic liquid composite particles.Be 0.05mmol/L, contain 2,6-Dichlorophenol, 2 respectively in 100mL, concentration, in the pollutant water bodys such as 4-Dichlorophenol or 2,3-Dichlorophenol, add 1g magnetic Nano immobilization laccase and ionic liquid composite particles, at room temperature reacted 4 hours.Removal of pollutants rate (%) is as shown in table 4 in the water body, and table 4 is the result show, magnetic Nano immobilization laccase and ionic liquid composite particles can effectively be removed the pollutant in the water body.
Table 4 embodiment 4 gained composite particles are to pollutants removal rate in the water body
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. preparation method based on magnetic Nano immobilization laccase and ionic liquid composite particles is characterized in that comprising following operating procedure:
(1) the nano magnetic silica particulate of the surperficial amino functional of preparation: octyl ether, oleic acid and carbonyl iron are mixed; be heated to 90～140 ℃, reacted 1～4 hour, be cooled to room temperature; add the dry oxidation trimethylamine; under nitrogen protection, be heated to 120～150 ℃, react after 1～3 hour; be cooled to room temperature; add ethanol, centrifugation, gained is precipitated as magnetic γ-Fe
2O
3Nano particle; With magnetic γ-Fe
2O
3Nanoparticulate dispersed is in n-hexane, and obtaining concentration is magnetic Nano γ-Fe of 0.5g/mL
2O
3Solution; With magnetic Nano γ-Fe
2O
3Solution, polyoxyethylene nonylplenyl ether and n-hexane mix also ultrasonic dispersion 10 minutes, add ammoniacal liquor and ethyl orthosilicate, and at room temperature, stirring reaction 24～48 hours adds silane coupler again, at room temperature, and stirring reaction 12～48 hours; Centrifugation, solid phase are the nano magnetic silica particulate of surface amino groups functionalization.
(2) the nano magnetic silica particulate of surface amino groups functionalization and 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride joins in the laccase solution, and at room temperature stirring reaction is 12～48 hours; Magnetic Isolation, collecting solid phase is based on magnetic Nano silicon dioxide microparticle immobilization laccase.
(3) magnetic Nano silicon dioxide microparticle immobilization laccase and functionalized ion liquid mix, at room temperature, and stirring reaction 12～48 hours; Magnetic Isolation, collecting solid phase is magnetic Nano ionic liquid composite particles.
2. preparation method according to claim 1, it is characterized in that: the volume ratio of the described carbonyl iron of step (1) and octyl ether is 1:50～1:20, the mol ratio of described carbonyl iron and oleic acid is 1:3～1:6; The mol ratio of described carbonyl iron and dry oxidation trimethylamine is 1:3～1:5; The volume ratio of described carbonyl iron and ethanol is 1:100～1:300; The degree of polymerization of described polyoxyethylene nonylplenyl ether is 520; Described magnetic Nano γ-Fe
2O
3The volume ratio of solution, polyoxyethylene nonylplenyl ether and n-hexane is 1:(0.6～3): (12～30); Described nanometer γ-Fe
2O
3The volume ratio of solution and ammoniacal liquor, ethyl orthosilicate and silane coupler is 10:1:(3～6): (3～9); Described silane coupler is 3-aminopropyl triethoxysilane or N-β-(aminoethyl)-γ aminopropyl trimethoxysilane.
3. preparation method according to claim 1, it is characterized in that: the described laccase of step (2) is lacquer tree, adopt suede bolt bacterium, Corilus versicolor Quel. or crinosity bolt bacterium, laccase solution is for to be dissolved in pH7.5 sodium phosphate 0.1mol/L buffer solution with laccase, and preparation laccase concentration is 20mg/mL.
4. preparation method according to claim 1, it is characterized in that: the mass ratio of the nano magnetic silica particulate of the described surface amino groups functionalization of step (2), 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and laccase solution is 5:(1～3): (10～30).
5. preparation method according to claim 1, it is characterized in that: the mass ratio of step (3) described magnetic Nano silicon dioxide microparticle immobilization laccase and functionalized ion liquid is 1:5～1:10.
6. preparation method according to claim 1, it is characterized in that: the described functionalized ion liquid of step (3) prepares according to following operating procedure: be the N of 6:5 with mol ratio, N-carbonyl dimidazoles (CDI) and the ionic liquid that contains carboxyl mix, under 50 ℃, behind the stirring reaction 24 hours, be cooled to room temperature, obtain functionalized ion liquid.
7. preparation method according to claim 6, it is characterized in that: the described ionic liquid that contains carboxyl is 1-carboxyethyl-3-methyl imidazolium tetrafluoroborate, 1-carboxyethyl-3-methylimidazole hexafluorophosphate, 1-carboxyethyl-3-methylimidazole trifluorosulfonimide salt, 1-carboxylic propyl group-3-methyl imidazolium tetrafluoroborate or 1-carboxylic propyl group-3-methylimidazole hexafluorophosphate.
One kind according to claim 1～7 each described method prepare based on magnetic Nano immobilization laccase and ionic liquid composite particles.
9. a kind of application in the pollutant in removing water body based on magnetic Nano immobilization laccase and ionic liquid composite particles according to claim 8.
10. application according to claim 9 is characterized in that: described application is in containing the water body of pollutant, adds based on magnetic Nano immobilization laccase and ionic liquid composite particles, at room temperature reacts 4 hours; Described pollutant is dyestuff, chlorophenol or phenol.
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